3-hydroxyquinophthalone diamido pigments



United States Patent M 3,374,238 3-HYDROXYQUINOPHTHALONE DIAMIDOPIGMENTS Arnold Wick, Therwil, and Christoph Frey, Basel, Switzerland,assignors to Ciba Limited, Basel, Switzerland, 2 Swiss company NoDrawing. Filed June 18, 1965, Ser. No. 465,157 Claims priority,application Switzerland, June 26, 1964, 8,416/64 8 Claims. (Cl. 260287)ABSTRACT OF THE DISCLOSURE Pigments of the 3-hydroxyquinophthaloneseries of the formula in which A represents an arylene residue,especially a benzene or naphthalene residue, R represents a direct bondor an organic residue and in which the benzene residue B may containfurther substituents, for example, halogen atoms or alkoxy groups.

The present invention provides valuable new pigments of the3-hydroxyquinophthalone series of the formula ECONHFR-NHCO-Ei o in whichA represents an arylene residue, especially a benzene or naphthaleneresidue, R represents a direct bond or an organic residue and in whichthe benzene residue B may contain further substituents, for example,halogen atoms or alkoxy groups.

Since the products of the invention are pigments they naturally must notcontain groups imparting solubility in water, particularly acid groupsimparting solubility in water, for example, sulphonic acid groups andcarboxylic acid groups.

The new pigments may be obtained by condensing a diarnine with amonocarboxylic acid halide of the formula J C COHal in which A and Bhave the meanings given above in a molar ratio of 1:2.

CONH-*RNHCO C I B a O ll 3,374,238 Patented Mar. 19, 1968 Themonocarboxylic acid halides used are preferably acid chlorides of thecarboxylic acids of the formulae (3) b cooa 7' ,1-c 6 0r (4) X E coonOH/C C C II 0 in which X and Y represent hydrogen or halogen atoms oralkyl groups, or X and Y together with two adjacent carbon atoms mayform the residue of a benzene ring.

The carboxylic acids of the Formulae 3 and 4 are obtainable bycondensing tri-mellitic anhydride or hemirnellitic anhydride with a2-methyl-3-hydroxyquinoline- 4-carboxylic acid, for example, with2-methyl-3-hydroxyqninoline-4-carboxylic acid,2methyl-3-hydroxy-5-chloroquinoline-4-carboxylic acid,

a 3 Z-methyl-3-hydroxy-5-methyl-8-methoxyquinoline4-carboxylic acid,2-methyl-3-hydroxy-6-chloro-7-bromo-8-rnethoxyquinoline-4-carboxylicacid,2-methyl-3-hydroxy-5-methyl-6-chloro-8-methoxyquinoline-4-carboxylicacid, 2-methyl-3-hydroxy-5 6-benzoquinoline-4-carboxylic acid,2-methyl-3-hydroxy-6 7-benzoquinoline-4-carboxylic acid and2-methyl-3-hydroxy-7 8-benzoquinoline-4-carboxylic acid.

Conversion of the carboxylic acids into their acid halides can becarried out in the usual manner by treatment with acid halogenatingagents, especially thionyl chloride. Treatment with the acidhalogenating agents is advantageously carried out in an inert organicsolvent, for example, dimethylformamide, a chlorobenzene, for example,monochlorobenzene or dichlorobenzene, toluene, xylene or nitrobenzene.Dimethylformamide may also be added when working with any of the fivelast-mentioned solvents.

The diamines to be used in accordance with the invention are, forexample, hydrazine or aliphatic diamines, for example, ethylenediamine,heterocyclic diamines, but preferably aromatic diamines, especiallythose of the benzene, diphenyl and naphthalene series. Diamines thathave been found to be specially suitable are those of the formulae N H2Xi in which X and X represent hydrogen or halogen atoms, alkyl, alkoxy,carbalkoxy, carbamide or nitro groups and Y, represents hydrogen orhalogen atoms, alkyl or alkoxy groups. The following diamines may bementioned as examples:

1:2-diaminobenzene,

2-diamino-4-nitrobenzene,

' 3-diaminobenzene, :3-diamino-Z-methylbenzene,

:3 -diamino-4-methylbenzene, :3-diamino-4-chlorobenzene, :3-diamino-26-dimethylbenzene, :3-diamino-4 6-dimethylbenzene, :3-diamino-2S-dichlorobenzene, :3-diamino-4 6-dichlorobenzene,

: 3-diamino-4 :5 6-trichlorobenzene, :3-diamino-5-carbomethoxybenzene,:3-diamino-5 -carbanilidobenzene, :4-diaminobenzene,:4-diamino-2-chlorobenzene, :4-diamino-2-bromobenzene,:4-diamino-2:S-dichlorobenzene, :4-diamino-Z-methylbenzene, :4-diamino-2S-dirnethylbenzene, z4-diamino-2-methoxybenzene, .4-diamino-2 5-dimethoxybenzene,

4-diamino-2 S-diethoxybenzene,

. 4-diamino-2-chloro-5 -methylbenzene,:4-diamino-2-chloro-5-methoxybenzene,:4-diamino-2-methyl-5-methoxybenzene, :4'-dian1inodiphenyl,

:3 -dichloro-4 4'-diamin0diphenyl,

3'-dimethyl-4 4'-diaminodiphenyl,

3 '-dimethoxy-4 4'-diaminodiphenyl,

3' 5 5-tetrachloro-4:4'-diaminodiphenyl,

2' 5 5-tetrachloro-4 :4'-diaminodiphenyl, :3'-dichloro-55-dimethyl-4:4-diaminodiphenyl,

4'-diaminodiphenylether,

1: 1. 1 1 1 1 1 l 1 l 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4 3 3 3 3 2 3 4:4:4'-diaminodiphenylketone,

4:4-diaminodiphenylsulphone,

3 :3 -diaminodiphenylsulphone,

4:4-diaminodiphenylmethane,

3 3-diaminodiphenylmethane,

3 :3 -diamino-4 4-dimethyldiphenylmeth ane,

3 3'-diamino-4:4'-dichlorobenzil,

4:4 diamino-2z5:2:5'-tetrachlorodiphenylurea,

di-(4-aminobenzenesulphonyl)-methylimide,

4-(4'-aminobenzoylamino)-aminobenzene,

4:4-diaminodiphenylformylamine,

4-aminobenzoic acid-4'-aminophenylester,

2:8-diaminochrysene,

3 :S-diaminopyrene,

3 IO-diaminopyrene,

4: 1 l-diaminofiuoroanthene,

2 6- or 1:5-diaminonaphthalene,

2:6-, 1:4- or 1:S-diaminoanthraquinone,

diaminobenzthiazoles, for example 2-(4'-aminophenyl)-6-aminobenzthiazole,

2:6-diaminopyridine,

2:6-diarninopyrimidine,

3 :5 -diamino-1-methyl-2 4: 6'triazine, and

3 2 3-diaminodibenzofuran.

Condensation between the carboxylic acid halides of the kind definedabove and the diamines is advantageously carried out in an anhydrousmedium. Under these conditions it proceeds surprisingly easily, even attemperatures within the boiling range of the common organic solvents forexample toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene,nitrobenzene and the like. To accelerate the reaction it is generallyadvantageous to use an agent capable of binding acid, for example,anhydrous sodium acetate or pyridine. Some of the pigments obtained arecrystalline and some are amorphous and most of them are obtained in avery good yield and in a pure state. It is advantageous to isolate theacid chlorides which have been obtained from the carboxylic acids but insomecases, however, isolation of the acid chlorides can be omittedwithout harm and condensation carried out immediately following theformation of the carboxylic acid chlorides.

The new products are valuable pigments which can be used for a very widevariety of purposes. For example, they can be used in a state of finedivision for the spincolouration of filament and staple fibre viscoserayon, cellulose ethers and esters, polyarnides, polyurethanes andpolyesters, as well as in the preparation of coloured lacquers and likeformers, solutions and products made from cellulose acetate,nitrocellulose, natural resins and synthetic resins, for example,polymerization resins and condensation resins, for example, aminoplasts,alkyd resins, phenoplasts, polyolefines, for example, polystyrene,polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile andfrom rubber, casein, silicones and silicone resins. They can also beused with advantage in the preparation of coloured pencil and laminatedsheet material.

The following examples illustrate the invention.

Example I 7.03 parts of 3-hydroxyquinophthalone-S-carboxylie acidchloride of the formula (prepared in accordance with United Statespatent specification No. 3,023,214 granted to E. I. du Pont de Nemoursand Company, Wilmington, Del., a corporation of Delaware, on Feb. 27,1962, Example 7, by heating trimellitic acid anhydride with2-mcthyl-3-hydroxyquinoline-4-carboxylic acid in orthodichlorobenzeneand converting the carboxylic acid into the acid chloride by means ofthionyl chloride) were heated to 100 to 110 C. in 250 parts of anhydrousortho-dichlorobenzene and 0.05 part of thionyl chloride. A solution of1.08 parts of'lz4-diaminobenzene in about 50 parts of anhydrousorthodichlorobenzene at 100 to 110 C. and 0.1 part of anhydrous pyridinewere added and the whole heated for to 6 hours at 140 to 160 C. Thereaction mixture was allowed to cool to 100 C., filtered, and the filterresidue washed with orthodichlorobenzene having a temperature of 10010120 C. until the washings ran almost colourless, with methanol and waterand the pigment so obtained dried in vacuo at 90 to 100 C. Ayellow-orange powder was obtained. When this powder was converted into astate of fine division and Worked into polyvinyl chloride on a rollermill it produced a yellow film having a good fastness to migration andto light.

In column II of the following table are listed the tints of polyvinylchloride films coloured with the pigments obtainable by condensing theacid chloride used in Example 1 with the diamines listed in column I.

Column I Column II 1 4: 4-diaminophenyl Yellow. 2. 3:3'-dimethoxy-4:4-diaminodiphenyl. Yellow-orange. 3.4:4-diaminodiphenylsulphone Yellow. 4. 2 diohloro-l:4-diaminobenzene.Do. 5. 3: 3 -diohloro-4:4-diaminodiphenyl. Do. 6. 1 5-diaminonaphthaleneD0. 7. 1 :2-diaminobenzene Do.

2: 5-dirnethoxy-1 :4-diamlnobenzene Yellow-orange 3: S-diaminopyreneellow. 10. 4(4-aminobenzoylami.no)-1-am1nobenzene Do. 11.3:3-diaminodiphenylsulphone Reddish yellow.

12. 4:4-diaminodiphenylformylamine- Yellowish brown.

13. 2methyl-5eh1oro-1:4-diaminobenzene. Greenish yellow. 14. 2:5-diethoxy-l :4-diaminobenzene Orange. 15. :5-dimethyl-1:t-diaminobenzeno Greenish yellow. 16. 4-arninobenzoicaeid-4-arninophenylester. Yellow. 17. 3 :3-diInethyl-4:4-diaminodiphenylDo. 18. 1:2-diamino-4-i1itrobenzene Do. 19. 1 z3-diamino4methylbenzene.Do. 20. 1 :3-diamino4: Edimethylbenzene Do. 21. 1 :3-diamino-4: 5:fi-trichlor'obenzene. D0. 22. 1 :3-diamino-5-earbornethoxybenzene. Do.23. 1:3-diamino-5-earban ilidobenzene Reddish yellow. 24. 3:3-dimethyl-4:4-dlaminodiphenyl. ellow. 25. 4:4-diannnodiphenylether Do.6 3: -diaminodiphenyl.methane... D0. 4 diaminodiphenylmethane Do. 28- 3.diamino-4:4"dirnethyldiphenylmethane. Do. 29. 3:3-diarm'no-4:4'-dichlorobenzil Do. 30. 4:4-diamino-2: 5: 2:5'-tetrach1orodiphenyl- D0.

urea. 31 Di-(taminobenzenesulphonyl)-methylimide- Do. 32. 310-diamin0pyrene Do. 33. 1:4-diaminoanthraquinone- Brown. 34- 1S-diaminoanthraquino ne Yellow-brown. 35. 2: G-diaminoanthraquinone.Yellow. 2: 6-diaminopy1idine Do. 3: 5-diamino-1-methyl-2 4: 6 Do. 8. 3:3-diaminodibenzofuran- Do. 39. Ethylenediarnine o. o.

30- Hydrazine A Example 2 5.1 parts of 3'-hydroXy-6:8'-dibromoquinophthalone- S-carboxylic acid chloride of theformula (IL COC1 NII Br 0 (prepared by heating2-methyl-3-hydroxy-6:S-dibromoquinoline-4-carboxylic acid withtrimellitic acid anhydride in ortho-dichlorobenzene and converting thecarboxylic acid into the acidchloride by means of thionylchloride) wereheated to 100 to 110 C. in 120 parts of nitroben- Zene and 0.02 part ofthionyl chloride. A solution of 0.92 part of 4:4 diaminodiphenyl inabout 50 parts of nitrobenzene at 100 to 120 C. and 0.8 part of pyridinewere added and the whole heated for 5 to 6 hours at 140 to 160 C(whilestirring well. The reaction mixture was cooled to about 120 C., filteredand the filter residue well washed with hot nitrobenzene. It was thenwashed successively with methanol and Water and the pigment so obtaineddried in vacuo at to C. When this powder was converted into a state oftime division and worked into polyvinyl chloride on a roller mill itproduced a yellow film having a good fastness to migration and to light.

In column II of the following table are listed the tints of polyvinylchloride films coloured with pigments obtainable by condensing the acidchloride used in Example 2 with the diamines listed in column I.

I II

1 1 :4-diam1nobenzene R eddish yellow. 2 4 4-diaminodiphenyl Yellow.

3- 3 :3-di.methoxy-4: 4-dlaminod heny Do.

4 3: 3-dichloro-4 4-diaminodlphenyl Do.

5 2-methoxy-5-chloro-1:4-diaminobenzene.. Do.

6 2: 5-dimethoxy-1 4-dlaminobenzene Yellowish brown 7 1 B-dimethyl-:fi-diaminobenzene... Yellow.

8-.... Hydrazine Do.

Example 3 Example 4 3.86 parts of3-hydroxy-6-chloroquinophthalone-5-carboxylic acid chloride of theformula Nrr GOCl

(prepared by heating 6-chloro-2-methyl-3-hydroxyquino line-4-carboxylicacid with trirnellitic acid anhydride in orthodichlorobenzene andconverting the carboxylic acid into the acid chloride by means ofthionyl chloride) were heated at 100 to C. in parts of nitrobenzene and0.02 part of thionyl chloride. A solution of 0.54part of1:4-diaminobenzene and 0.8 part of pyridine in about 50 parts ofnitrobenzene was added and the whole heated at to C. for 5 to 6 hours.The reaction mixture was cooled to about 120 C., filtered and thepigment washed successively with hot nitrobenzene, cold methanol andwater and then dried in vacuo at-"a'bout 100 C. A yellow powder wasobtained. When this powder was converted into a state of fine divisionand worked into polyvinyl chloride on a roller mill it produced a yellowfilm having a good fastness to migration and to light.

In column II of the following table are listed the tints of polyvinylchloride films coloured with the pigments obtainable by condensing theacid chloride used in Example 4 with the diamines listed in column I.

I II

1 1:3-dimethyl-4:G-diamlnobenzene Yellow. 22:5-dlchloro-1:4-diaminobenzene..... Yellow-orange. 33:3-dichloro-4:4-diaminodiphenyl Yel w. 43z3-dimethoxy-4:4-dlam1nodiphenyl Reddlsh yellow.

in that example. The yellow powder so obtained was converted into astate of fine division and worked into polyvinyl chloride on a rollermill. A yellow film having a good fastness to migration and to light wasobtained.

In column II of the following table are listed the tints produced withthe pigments obtainable by condensing 3-hydroxy 6bromoquinophthalone-S-carboxylic acid chloride with the diamines listedin column I.

I II

4:4-diamlnodiphenyl Yellow 3: 3-d iehloro-4 4'-diamlnodiphenyl Do 4.0parts of 3-hydroxy-6'-chloro-8'-methylquinophthal one-S-carboxylic acidchloride of the formula i or on c cc1 1:0 I N1 on. 0

(prepared by heating6-chloro-2:8-dimethyl-3-hydroxyquinoline-4-carboxylic acid withtrimellitic acid anhydride in ortho-dichlorobenzene and converting thecarboxylic acid into the acid chloride by means of thionyl chloride)were condensed with 0.54 part of 1:4-diaminobenzene in the mannerdescribed in Examples 2 and 4. A yellow powder was obtained. When thispowder was converted into a state of fine division and worked intopolyvinyl chloride on a roller mill it produced a yellow film having agood fastness to migration and to light.

In column II of the following table are listed the tints of polyvinylchloride films coloured with the pigments obtainable by condensing theacid chloride used in Example 6 with the diamines listed in column I.

Example 7 3.7 parts of 3'-hydroxy-6':8dimethylquinophthalone-S-carboxylic acid chloride of the formula (prepared by heating2:6:8-trimethyl-3-hydroxyquinoline- 4-carboxylic acid with trimelliticacid anhydride in orthodichlorobenzene and converting the carboxylicacid into the acid chloride by means of thionyl chloride) were condensedwith 1.22 parts of 3:3'-dimethoxy-4:4-diaminodiphenyl in the mannerdescribed in Examples 2 and 4. An orange powder was obtained. When thispowder was converted into a state of fine division and worked intopolyvinyl chloride on a roller mill it produced a reddish yellow filmhaving a good fastness to migration and to light.

When the 1.22 parts of 3:3'-dimethoxy-4:4'-diaminodiphenyl used inExample 7 were replaced by 1.275 parts of3':3'-dichloro-4:4'-diaminodiphenyl or by 0.99 part of3:3'-diaminodibenzofuran, the pigments obtained pro- 8 duced a reddishyellow tint and a yellow tint respectively when worked into polyvinylchloride film.

Example 8 4.02 parts of 3'-hydroxy-7:8'-benzoquinophthalone-S-carboxylic acid chloride of the formula NLI (prepared by heating2-methyl-3-hydroxy-7:8-benzoquinoline-4-carboxylic acid with trimelliticacid anhydride in orthodichlorobenzene and converting the carboxylicacid into the acid chloride by means of thionyl chloride) were condensedwith 0.92 part of 4:4-diaminodiphenyl in a manner analogous to thatdescribed in Examples 2 and 4. An orange powder was obtained. When thispowder was converted into a state of fine division J and worked intopolyvinyl chloride on a roller mill it produced a yellow film having agood fastness to migration and to light.

Further pigments were obtained by condensing the acid chloride used inExample 8 with the diamines listed in column I of the following table.The tints of polyvinyl chloride films coloured With these pigments areindicated in column II.

Example 9 17.8 parts of 3-hydroxyquinophthalone-4-carboxylic acidchloride of the formula 6 C001 on o l NI'I were stirred into 500 partsof anhydrous nitrobenzene and a hot solution of 4.42 parts of2:5-dichloro-paraphenylenediamine in 250 parts of anhydrous nitrobenzeneadded. 1 part of absolute pyridine was then added and the batch heatedto 140 C. in the course of 2 hours and stirred at that temperature for17 hours. After coding the reaction mixture to C. the dyestutf whichprecipitated in the form of crystals was isolated by suction filtrationand washed with parts of nitrobenzene at 100 C. The product was thensuspended in 1,000 parts of ortho-dichlorobenzene, the suspensionstirred for half an hour at C., suction-filtered while hot, the filterresidue washed successively with hot ortho-dichlorobenzene and hotethanol and then dried in vacuo at 80 C. A yellow orange powder wasobtained. When this powder was converted into a state of fine divisionand worked into polyvinyl chloride on a roller mill it produced a yellowfilm having an excellent fastness to migration and a high fastness tolight.

In column II of the following table are listed the tints of polyvinylchloride films coloured with the pigments obtainable by condensing in ananalogous manner the above-mentioned acid chloride with the diamineslisted in column I.

1 3:3-dimethoxy-4:4-diaminodiphenyl Yellow. 23:3-dichloro-4:4-diaminodiphanyl .Do.

The acid chloride of the hitherto unknown 3'-hydr0xy- 5 plateletsmelting at 318 to 319.5 C. Elementary analysis gave the following.

Calculated: C, 68.47%; H, 3.33%; N, 4.20%. Found: C, 67.9%, H, 3.7%; N,4.5%.

Example 10 A mixture was prepared from 65 parts of polyvinyl chloride,parts of dioctyl phthalate and 0.2 part of the pigment obtained in themanner described in the first paragraph of- Example 1. This mixture wasthen worked to and fro for 7 minutes at 140 C. on a two-roller mill. A35 yellow film having a very good fastness to light and to migration wasobtained.

Example 11 0.25 part of the pigment obtained in the manner described inthe first paragraph of Example 1, 40 parts of an alkydmelamine stovingenamel containing of solid substance and 4.75 parts of titanium dioxidewere ground for 24 hours in a rod mill. A thin layer of the enamel soobtained was applied to aluminium foil and 10. stoved for one hOur at120 C. A yellow coating having an excellent fastness to light wasobtained.

Example 12 99 parts of w-caprolactam polya-mide in the form of chipswere dry-coated with one part of the pigment obtained in the mannerdescribed in the first paragraph of Example 1, the pigment being in astate of very fine division. The coated chips were then spun in theusual manner, for example, by the grid-spinning process at 0 about 260C.The yellow filaments so obtained displayed an excellent fastness tolight and to wet treatments.

What is claimed is: 1. A 3-hydroxyquinophthalone pigment of the formula-3. C i H. X I @CONHRNHOC@/ \Cq/fl Y I it in which. R is a benzene,diphenyl or naphthalene group, X and.Y are hydrogen, chlorine, bromineor methyl or X and Y when in o-position to each other together with twoadjacent carbon atoms are a benzene ring.

2. 3hydroxyquinophthal-one pigments as claimed in 0 claim 1, wherein Ris the group of the formula in which Y is hydrogen, halogen, lower alkylor lower alkoxy.

3. 3-hydroxyquinophthalone pigments as claimed in claim 1, wherein R isthe group of the formula in which X and X are hydrogen, chlorine,bromine, lower alkyl, lower alkoxy, carbalkoxy, caubamido or nitro.

4. The pigment of the formula or 31 o -o ONH-NHC oq N/\/ 11 (IL 5. Thepigment of the formula CH3 01 OH I HO o1 OONHNHOO \N N 1 H 41H: H H CH3I CH3 6. The pigment of the formula o 01 or 0 Br OH HO B.r

{ -o O-NH NI-IC 0- N N/ H H l Br 15 7. The pigment of the formula 8. Thepigment of the formula I v i win ml-I}, 0 coNu -Nu-oo o I v OH I v l HOUN v H i 0 0 References Cited 3,023,213 2/ 1962 Richter 260287 UNITEDSTATES PATENTS 3,02 ,214 2/1962 Richter 260-287 2,914,542 11/1959Randall et a1 26()368 X 25 ALEX MAZEL, primmy Examiner 2,985,656 5/1961Weber et a1 260-329.2 X

3,023,212 2/1962 Richter 260-287 D m

